JP3031036B2 - Fluorinated aromatic diamine compound, fluorinated diamine compound in which amino group is protected, and methods for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing aromatic diamine compound, a fluorine-containing diamine compound in which an amino group is protected, and a method for producing the same.

[0002]

2. Description of the Related Art Condensation polymers such as polyimide and polyamide have excellent heat resistance and are used in a wide range of fields from electronic materials to aerospace materials. In recent years, in these fields, materials having various high performances and high functions in addition to excellent heat resistance have been required. For example, in the field of electronic materials, reduction in moisture absorption and dielectric constant and improvement in transparency are required. However, a material that can sufficiently meet these demands for high performance has not been obtained so far.

In order to obtain a polymer satisfying such requirements, a substituent containing many fluorine atoms is introduced into the molecular structure of the aromatic diamine, which is a monomer, as a substituent exhibiting these properties. Is considered to be effective.

Conventionally, examples of aromatic diamines into which perfluoroalkyl groups containing many fluorine atoms have been introduced include:
Japanese Patent Application Laid-Open No. 1-190562 discloses

Embedded image [Wherein, Rf ′ represents a perfluoroalkyl group in Chemical Formula 5].

[0005] Also, Japanese Patent Application Laid-Open No. 1-180860 discloses that
Chemical 6

Embedded image Is shown.

[0006]

SUMMARY OF THE INVENTION The above-mentioned JP-A-1-190
No. 562 discloses only an example of producing an aromatic diamine having a trifluoromethyl group as a perfluoroalkyl group as a substituent. In this case, the fluorine content is low, and the required performance is not exhibited. difficult.

The aromatic diamine disclosed in JP-A-1-180860 has a methylene group having a small bond dissociation energy between a benzene ring and a perfluoroalkyl group. It was easy to cut and had poor heat resistance.

Accordingly, the present inventors have proposed a fluorine-containing aromatic diamine compound having a perfluoroalkenyloxy group introduced into a molecular structure as a substituent having many fluorine atoms,
It provides intermediates and methods for their preparation.

[0009]

Means for Solving the Problems The fluorine-containing aromatic diamine compound in the present invention is represented by the following formula (I):

Embedded image [However, in the general formula (I), Rf is, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, are appropriate branches May be, hydrogen of the benzene ring is a lower alkyl group, a lower alkoxy group, fluorine,
Optionally substituted with a substituent such as chlorine or bromine.
Each amino group is bonded to the ortho, meta, or para position with respect to the ester bond].

The compound represented by the general formula (I) includes
Bis (4-aminophenyl ester) 5- (perfluorononenyloxy) isophthalate, bis (2-methyl-4-)-5- (perfluorononenyloxy) isophthalate
Aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-methoxy-4-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-fluoro-4-aminophenyl) Ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-chloro-4-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-bromo-4-aminophenyl ester) 5- (perfluorononenyloxy) isophthalic acid bis (3-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-amino-5-methylphenyl ester), 5- (perfluoro Nonenyloxy) isophthalic acid bis (3-amino-5)
-Methoxyphenyl ester), bis (3-amino-5-fluorophenyl ester) 5- (perfluorononenyloxy) isophthalate, bis (3-amino-chlorophenyl ester) 5- (perfluorononenyloxy) isophthalate , 5- (Perfluorononenyloxy)
Bis (3-amino-5-bromophenyl ester) isophthalate, bis (2-aminophenyl ester) isophthalate, bis (2-aminophenyl ester) isophthalate, bis (2-aminophenyloxy) isophthalate Amino-4-methylphenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-amino-
Bis (2-amino-4-ester), 5- (perfluorononenyloxy) isophthalic acid
Fluorophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-amino-4-chlorophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-amino-4-bromophenyl ester) ), 5- (perfluorohexenyloxy) isophthalic acid bis (4-aminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-methyl-4-aminophenyl ester), 5- (perfluorohexenyl) Oxy) isophthalic acid bis (2-methoxy-4-aminophenyl ester), 5- (perfluorohexynyloxy) isophthalic acid bis (2-fluoro-4-aminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid Acid bis (2-chloro-4-amido Phenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-bromo-4-aminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-aminophenyl ester), 5- (per Fluorohexenyloxy) isophthalic acid bis (3-amino-5-methylphenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-amino-5-methoxyphenyl ester), 5- (perfluorohexynyloxy) ) Bis (3-amino-) isophthalate
5-fluorophenyl ester), bis (3-amino-5) 5- (perfluorohexenyloxy) isophthalate
-Chlorophenyl ester), bis (3-amino-5-bromophenyl ester) 5- (perfluorohexenyloxy) isophthalate, bis (2-aminophenyl ester) 5- (perfluorohexenyloxy) isophthalate, 5- ( Perfluorohexenyloxy) isophthalic acid bis (2-amino-4-methylphenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-amino-4-methoxyphenyl ester), 5- (perfluorohexynyl) Oxy) isophthalic acid bis (2-amino-4-fluorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-amino-4-chlorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-amino-4- Romo phenyl ester)
and so on.

In these compounds, a perfluorononenyl group means that Rf in the general formula (I) is -C ₉ F ₁₇
The a is ,, perfluoroalkyl hexenyl ones are those Rf in the general formula (I) is -C ₆ F _11, it is the same or less.

In the compounds exemplified above, compounds having a -C ₁₀ F ₁₉ group, a -C ₁₂ F ₂₃ group, or the like in place of the perfluorononenyl group or the perfluorohexenyl group can also be exemplified.

In the present invention, the fluorinated aromatic diamine compound represented by the general formula (I) is represented by the following formula [8]

Embedded image [However, the general formula (II) Medium Rf, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, optionally appropriately branched The hydrogen of the benzene ring may be appropriately substituted, and the hydrogen of the benzene ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, or bromine. R ¹
Is a monovalent organic group, R ² is hydrogen, and the monovalent organic group is
R ³ OC (＝ O) — group which protects an amino group
(Where R ³ is a monovalent organic group, a benzyl group, t-
Butyl group, p-methoxybenzyl group, p-nitrobenzyl
Group, p-biphenylisopropyl group, 9-fluorenyl
Shows the Rumechiru group), R ⁴ C (= O) - group (wherein R ⁴ represents hydrogen, an alkyl group or an aryl group), shows a trityl group, p- toluenesulfonyl group, further, R ¹ and R ² Represents a divalent —C (＝ O) —C ₆ H ₄ —C (＝ O) — group, and the nitrogen atom is bonded to the ortho, meta or para position with respect to the ester group. Wherein the amino-protected fluorinated diamine is subjected to a deprotection reaction of the protective group.

[0014] In the general formula (II), 2-valent organic group combined monovalent organic group or R ¹ and R ² as R ¹ is a group protecting the amino group, e.g., R ³ OC (= O) - group (wherein, R ³ is a monovalent organic group) may, specifically, benzyloxycarbonyl group, t- butyl oxy <br/> carbonyl group, p- methoxybenzyloxycarbonyl Examples include a carbonyl group, a p-nitrobenzyloxycarbonyl group, a p-biphenylisopropyloxycarbonyl group, and a 9-fluorenylmethyloxycarbonyl group. Examples of the group for protecting the amino group further include an R ⁴ C (＝ O) — group (where R ⁴ represents hydrogen, an alkyl group or an aryl group),
There are a trityl group, a p-toluenesulfonyl group, a group represented by the following formula 9, and the like.

Embedded image

Examples of the fluorinated diamine represented by the general formula (II) in which the amino group is protected include 5- (perfluorononenyloxy) isophthalic acid bis (4-benzyloxycarbonylaminophenyl ester) and 5- (perfluorononenyloxy) isophthalic acid. (Perfluorononenyloxy) isophthalic acid bis (2-methyl-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (4-methoxy-4-benzyloxycarbonylaminophenyl ester) ), 5- (perfluorononenyloxy) isophthalic acid bis (2-fluoro-4-benzyloxycarbonylaminophenyl ester), 5
-(Perfluorononenyloxy) isophthalic acid bis (2-chloro-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-bromo-4-benzyloxycarbonylaminophenyl) Ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-benzyloxycarbonylaminophenyl ester), 5-
Bis (perfluorononenyloxy) isophthalate (3
-Benzyloxycarbonylamino-5-methylphenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-methoxyphenyl ester), 5- (perfluorononenyloxy) isophthal Acid bis (3-benzyloxycarbonylamino-5-fluorophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-chlorophenyl ester), 5- (perfluorononenyl) Oxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-bromophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-benzyloxycarbonylaminophenyl ester), 5
-(Perfluorononenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-methylphenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-methoxyphenyl) Ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-fluorophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino- 4
-Chlorophenyl ester), bis (2-benzyloxycarbonylamino-4-bromophenyl ester) 5- (perfluorononenyloxy) isophthalate, 5-
(Perfluorohexenyloxy) isophthalic acid bis (4-benzyloxycarbonylaminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-methyl-4-benzyloxycarbonylaminophenyl ester), 5- (per Fluorohexenyloxy) isophthalic acid bis (2-methoxy-4-benzyloxycarbonylaminophenyl ester), 5
-(Perfluorohexenyloxy) isophthalic acid bis (2-fluoro-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-chloro-4-benzyloxycarbonylaminophenyl ester) 5- (perfluorohexenyloxy) isophthalic acid bis (2-bromo-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylaminophenyl ester), 5 -(Perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-methylphenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbo) Arylamino-5-methoxyphenyl ester), 5- (perfluoro hexenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino -
5- (fluorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-chlorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino) −5-
Bromophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-benzyloxycarbonylaminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-methylphenyl) Ester), bis (2-benzyloxycarbonylamino-4-)-(perfluorohexenyloxy) isophthalate
Methoxyphenyl ester), bis (2-benzyloxycarbonylamino-4-fluorophenyl ester) 5- (perfluorohexenyloxy) isophthalate,
5- (perfluorohexenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-chlorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-bromophenyl ester) ,and so on. In the compounds exemplified above, a t-butyloxycarbonyl group, a p-methoxybenzyloxycarbonyl group, a p-nitrobenzyloxycarbonyl group, a p-biphenylisopropyloxy group is used instead of the benzyloxycarbonyl group which is a protecting group for an amino group. Carbonyl group,
9-fluorenylmethyloxycarbonyl group, the R ⁴
Compounds having a group such as a C (= 0)-group, a trityl group, a p-toluenesulfonyl group, a group of the above-mentioned formula 9 and the like can be similarly exemplified.

The above deprotection reaction can be carried out as follows. Ethyl acetate, dimethylformamide, dimethylacetamide, a compound represented by the general formula (II),
A method in which hydrogen gas is passed through a solution dissolved in an organic solvent such as benzene, xylene, acetone, or tetrahydrofuran at 0 to 100 ° C. (particularly preferably around room temperature) in the presence of a catalyst such as palladium carbon (the amount of catalyst used is generally The amount of the compound represented by the formula (II) is preferably 1 to 50% by weight, and the time for passing hydrogen gas may be determined as appropriate, but usually 1 to 10 hours is sufficient.) Is dissolved in the organic solvent as described above, and HF, HBr, HC
1. A method in which a hydrogen acid such as H ₂ SO ₄ is added and reacted (hydrogen acid is preferably used in an amount of 1 to 50 times equivalent to the compound represented by the general formula (II). Is preferably reacted at room temperature or lower, particularly at 0 ° C. or lower, and other hydrogen acids are preferably reacted at 0 to 100 ° C., particularly at about room temperature.
Usually, 0.1 to 1 hour when HF is used, and 1 to 10 hours when other hydrogen acid is used is sufficient), and the compound represented by the general formula (II) is converted into sodium hydrogen carbonate,
A method in which the reaction is carried out in the presence of a basic compound such as potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and water (the basic compound and water are each 1 to 50 to the compound represented by the general formula (II)). It is preferable to use a double equivalent, and the reaction may be carried out using water, an alcohol such as methanol or ethanol, cresol or the like as a solvent, in addition to the organic solvent described above.

The fluorinated diamine compound having a protected amino group represented by the general formula (II) is represented by the following formula (III):

Embedded image [However, the general formula (III) Medium Rf, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, optionally appropriately branched And the hydrogen of the benzene ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine, etc.] and an acid chloride compound represented by the general formula (IV) ]

Embedded image [However, in the general formula (IV), R ¹ is a monovalent organic group, R ² is hydrogen, the monovalent organic group is a group for protecting an amino group, and R ³ OC (＝ O) — Group (where R ³ is a monovalent organic group
Benzyl group, t-butyl group, p-methoxyben
Jyl group, p-nitrobenzyl group, p-biphenylisop
Ropyl group, 9-fluorenylmethyl group) , R ⁴ C
(= O) - group (wherein R ⁴ represents hydrogen, an alkyl group or an aryl group), shows a trityl group, p- toluenesulfonyl group, further, R ¹ and R ^2, divalent -C (= O)-
A C ₆ H ₄ —C (＝ O) — group, wherein hydrogen on the benzene ring is
A lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine and the like, which may be appropriately substituted, and the nitrogen atom is bonded to the ortho, meta or para position with respect to the hydroxy group.) It can be produced by a method characterized by reacting an aminohydroxybenzene compound in which the amino group represented is protected.

Examples of the acid chloride compound represented by the general formula (III) include 5- (perfluorononenyloxy) isophthalic acid dichloride, 4-methyl-5- (perfluorononenyloxy) isophthalic acid dichloride, Methoxy-5- (perfluorononenyloxy) isophthalic acid dichloride, 4-fluoro-5-
(Perfluorononenyloxy) isophthalic acid dichloride, 4-chloro-5- (perfluorononenyloxy) isophthalic acid dichloride, 4-bromo-5- (perfluorononenyloxy) isophthalic acid dichloride, 5- (perfluoro Hexenyloxy) isophthalic acid dichloride, 4-methyl-5- (perfluorohexenyloxy) isophthalic acid dichloride, 4-methoxy-5- (perfluorohexenyloxy) isophthalic acid dichloride, 4-fluoro-5- (perfluorohexenyloxy) ) Isophthalic acid dichloride, 4-chloro-5- (perfluorohexenyloxy) isophthalic acid dichloride, 4-bromo-5- (perfluorohexenyloxy) isophthalic acid dichloride and the like.

In these compounds, the perfluorononenyl group means that Rf in the general formula (III) is -C ₉ F ₁₇
The a is ,, perfluoroalkyl hexenyl ones are those Rf in the general formula (III) is -C ₆ F _11, it is the same or less.

In the compounds exemplified above, compounds having a -C ₁₀ F ₁₉ group, a -C ₁₂ F ₂₃ group or the like in place of the perfluorononenyl group or the perfluorohexenyl group can also be exemplified.

[0021] In the general formula (IV), 2-valent organic group combined monovalent organic group or R ¹ and R ² as R ¹ is a group protecting the amino group, such protecting group Are those described in the general formula (II).

As the aminohydroxybenzene compound represented by the general formula (IV) and having an amino group protected,
1-hydroxy-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-4- (t-butyloxycarbonylamino) benzene, 1-hydroxy-4-
(P-methoxybenzyloxycarbonylamino) benzene, 1-hydroxy-4- (p-nitrobenzyloxycarbonylamino) benzene, 1-hydroxy-4-
(P-biphenylisopropyloxycarbonylamino) benzene, 1-hydroxy-4- (9-fluorenylmethyloxycarbonylamino) benzene, 1-hydroxy-4- (acetylamino) benzene, 1-hydroxy-4- (4 -Toluenesulfonylamino) benzene, 1-hydroxy-4- (tritylamino) benzene 1-hydroxy-3-methyl-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-3-methoxy-4- (benzyloxycarbonyl) Amino) benzene, 1-hydroxy-3-fluoro-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-3
-Chloro-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-3-bromo-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-
3-methyl-4- (t-butyloxycarbonylamino) benzene, 1-hydroxy-3-methoxy-4-
(T-butyloxycarbonylamino) benzene, 1-
Hydroxy-3-fluoro-4- (t-butyloxycarbonylamino) benzene, 1-hydroxy-3-chloro-4- (t-butyloxycarbonylamino) benzene, 1-hydroxy-3-bromo-4- (t -Butyloxycarbonylamino) benzene, 1-hydroxy-3
-(Benzyloxycarbonylamino) benzene, 1-
Hydroxy-3- (t-butyloxycarbonylamino) benzene, 1-hydroxy-3- (p-methoxybenzyloxycarbonylamino) benzene, 1-hydroxy-3- (p-nitrobenzyloxycarbonylamino) benzene, 1- Hydroxy-3- (p-biphenylisopropyloxycarbonylamino) benzene, 1-
Hydroxy-3- (9-fluorenylmethyloxycarbonylamino) benzene, 1-hydroxy-3- (benzyloxycarbonylamino) -5-methylbenzene,
1-hydroxy-3- (benzyloxycarbonylamino) -5-methoxybenzene, 1-hydroxy-3-
(Benzyloxycarbonylamino) -5-fluorobenzene, 1-hydroxy-3- (benzyloxycarbonylamino) -5-chlorobenzene, 1-hydroxy-
3- (benzyloxycarbonylamino) -5-bromobenzene, 1-hydroxy-3- (t-butyloxycarbonylamino) -5-methylbenzene, 1-hydroxy-3- (t-butyloxycarbonylamino) -5 −
Methoxybenzene, 1-hydroxy-3- (t-butyloxycarbonylamino) -5-fluorobenzene, 1
-Hydroxy-3- (t-butyloxycarbonylamino) -5-chlorobenzene, 1-hydroxy-3- (t
-Butyloxycarbonylamino) -5-bromobenzene, 1-hydroxy-2- (benzyloxycarbonylamino) benzene, 1-hydroxy-2- (t-butyloxycarbonylamino) benzene, 1-hydroxy-
2- (p-methoxybenzyloxycarbonylamino)
Benzene, 1-hydroxy-2- (p-nitrobenzyloxycarbonylamino) benzene, 1-hydroxy-
2- (p-biphenylisopropyloxycarbonylamino) benzene, 1-hydroxy-2- (9-fluorenylmethyloxycarbonylamino) benzene, 1-hydroxy-2- (benzyloxycarbonylamino)-
4-methylbenzene, 1-hydroxy-2- (benzyloxycarbonylamino) -4-methoxybenzene, 1
-Hydroxy-2- (benzyloxycarbonylamino) -4-fluorobenzene, 1-hydroxy-2-
(Benzyloxycarbonylamino) -4-chlorobenzene, 1-hydroxy-2- (benzyloxycarbonylamino) -4-bromobenzene, 1-hydroxy-2
-(T-butyloxycarbonylamino) -4-methylbenzene, 1-hydroxy-2- (t-butyloxycarbonylamino) -4-methoxybenzene, 1-hydroxy-2- (t-butyloxycarbonylamino)- 4
-Fluorobenzene, 1-hydroxy-2- (t-butyloxycarbonylamino) -4-chlorobenzene, 1
-Hydroxy-2- (t-butyloxycarbonylamino) -4-bromobenzene and the like.

In the general formulas (I), (II) and (III), Rf in these formulas includes, for example, groups of the formulas (a) to (i) in the following formula (12).

Embedded image

An example of the compound represented by the general formula (III) is 5- (perfluorononenyloxy) isophthalic acid dichloride, and the following description will be made using this compound. The description below does not differ essentially for the other compounds represented. The reaction between 5- (perfluorononenyloxy) isophthalic acid dichloride and an aminohydroxybenzene compound having an amino group protected is described in Shinkagaku Koza Vol. 14 (II) (Maruzen Co., Ltd., issued on December 20, 1977). First
Known methods such as those shown on page 020 and below can be employed. For example, it is preferable to use a base such as pyridine, triethylamine, or dimethylaniline in order to react in a nitrogen atmosphere and capture generated hydrochloric acid. The base is preferably used in an amount of 1 molar equivalent to 3 molar equivalents with respect to the generated hydrochloric acid. If it is less than 1 molar equivalent, the capture of hydrochloric acid is insufficient, and if it is more than 3 molar equivalents, the yield may decrease due to side reactions and the like. Further, as a catalyst for accelerating this reaction, N, N-dimethylaminopyridine, 4-pyrrolidinopyridine, diazabicyclononene (DBN), diazabicycloundecene (DBU)
Strong bases such as can be used. The amount of catalyst used is
With respect to the base added to capture the hydrochloric acid, 0.
It is preferable to use 5 mol% to 200 mol%. The above reaction is preferably performed in an organic catalyst. As a solvent that can be used, an organic solvent having no reactivity with acid chloride and phenol such as toluene, benzene, and tetrahydrofuran ethyl ether is used. These organic solvents may be used as a mixture of two or more as long as they are compatible with each other. It is preferable to use a sufficiently dehydrated organic solvent. If water is present in the reaction system, the acid chloride is decomposed, and the yield may decrease. By the above reaction, a fluorinated diamine compound having an amino group protected and represented by the general formula (IV) is obtained. Or the reaction solution may be directly used for the next reaction in some cases.

5- (Perfluorononenyloxy) isophthalic acid dichloride is reacted with 5- (perfluorononenyloxy) isophthalic acid by a known method for acid chloride synthesis using thionyl chloride, phosphorus pentachloride, phosphorus trichloride or the like. To be obtained. The reaction conditions vary depending on the reagent used and are not particularly limited.

The above-mentioned 5- (perfluorononenyloxy) isophthalic acid is represented by the following general formula (V):

Embedded image (However, in the formula, the —C ₉ F ₁₇ group contains one double bond and may be appropriately branched).

In the general formula (V), the —C ₉ F ₁₇ group is
For example, it is introduced based on a hexamer of hexafluoropropene. The compound represented by the general formula (V) can be obtained, for example, by reacting a trimer of hexafluoropropene with 5-hydroxyisophthalic acid as disclosed in JP-A-60-511146. The reaction is carried out in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst, and is represented by the following general formula (VI).
The compound of the structural formula represented by is obtained.

Embedded image

The compounds obtained in each step are separated by column,
It can be purified by recrystallization from alcohol or the like.

[0029]

【Example】

(1) Synthesis of 5- (perfluorononenyloxy) isophthalic acid dichloride 61.2 g (0.1 mol) of 5- (perfluorononenyloxy) isophthalic acid of the above formula (VI) was added to thionyl chloride.
0 g (0.1 mol) was added and heated at 80 ° C. After 12 hours, the reaction became a homogeneous solution. After the excess thionyl chloride was distilled off under reduced pressure, vacuum distillation was carried out to obtain 5- (perfluorononenyloxy) isophthalic acid dichloride (yield 51%, boiling point of the obtained compound 140 ° C./3 mm)
Hg).

(2) Synthesis of 1-hydroxy-4- (benzyloxycarbonylamino) benzene 13.08 g (0.120 mol) of p-aminophenol
260 mL of dry tetrahydrofuran (THF) and 11.38 g (0.144 mol) of pyridine were added to the mixture. Under a nitrogen stream, a 30% toluene solution of benzyloxycarbonyl chloride was added dropwise over 1 hour on an ice bath. After completion of the dropwise addition, the reaction was carried out at 0 ° C. for 5 hours and at room temperature for 16 hours. The resulting pyridine hydrochloride was filtered off, the filtrate was evaporated down and concentrated, which was poured into a large amount of water and precipitated. The resulting white precipitate was filtered and dried under reduced pressure to obtain 1-hydroxy-4- (benzyloxycarbonylamino) benzene (yield 6).
5%). The ¹ H-nuclear magnetic resonance (NMR) spectrum (solvent acetone d ₆ , TMS standard) of this compound is as follows. ¹ H-NMR spectrum [solvent acetone d ₆ , TMS standard, δ (ppm)] 8.47 (s, 1H), 8.09 (s, 1H, NH, O
H), 7.45 to 7.30 (m, 7H), 6.77
(D, 2H, aromatic), 5.14 (s, 2H, CH 2 benzyl).

(3) Synthesis of bis (4- (benzyloxycarbonylaminophenylphenyl) 5- (perfluorononenyloxy) isophthalate) 11.7 g (48.0) of 1-hydroxy-4- (benzyloxycarbonylamino) benzene Mmol) dry T
Dissolved in 80 mL of HF, and 3.79 g of pyridine (48.
0 mmol), N, N-dimethylaminopyridine 0.4
9 g (4.0 mmol) were added. Here, under a nitrogen stream, 13.0 g (20.0 mmol) of 5- (perfluorononenyloxy) isophthalic acid dichloride in dry T
An HF solution (40 mL) was slowly added dropwise. After dripping,
The reaction was performed at room temperature for 5 hours and at 60 ° C. for 2 hours. The resulting pyridine hydrochloride was filtered off, the filtrate was evaporated down, concentrated and poured into a large amount of water. The resulting white precipitate was filtered, washed with water, and dried under reduced pressure to obtain 5- (perfluorononenyloxy) isophthalic acid bis 4- (benzyloxycarbonylaminophenyl ester) (yield 88%).
The infrared absorption (IR) spectrum and ¹ H-
The NMR spectrum was as follows. IR spectrum [KBr, ν (cm ^-1 )] 3380 (N-H), 1748 (C = O, ester),
1720 (C = O, urethane), 1548 (N-H),
1242 (CF). The spectrum is shown in FIG. ¹ H-NMR spectrum [solvent acetone d ₆ , TMS standard, δ (ppm)] 8.90 (s, 2H, NH), 8.85 (t, 1H),
8.11 (s, 2H, aromatic), 7.68 (d, 4
H), 7.42 to 7.28 (m, 14H, aromatic),
5.18 (s, 4H, benzyl CH _2).

The structural formula of bis (4- (benzyloxycarbonylaminophenyl ester) 5- (perfluorononenyloxy) isophthalate obtained above is represented by the following formula.

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(4) 5- (perfluorononenyloxy) isophthalic acid bis (4-aminophenyl ester)
Synthesis of 5- (perfluorononenyloxy) isophthalic acid bis 4- (benzyloxycarbonylaminophenyl ester) 10.6 g (0.010 mol) in THF 50 mL,
2.7 g of 5% palladium / carbon was added, and the mixture was stirred at room temperature for 7 hours under a hydrogen stream. After filtering off the palladium / carbon and evaporating the filtrate, the residue was subjected to column separation from ethyl acetate / hexane to obtain bis (4-aminophenyl ester) 5- (perfluorononenyloxy) isophthalate (yield). 63%).

Next, analysis data of the obtained bis (4-aminophenyl ester) of 5- (perfluorononenyloxy) isophthalic acid is shown. Melting point 149-150 ° C IR spectrum (KBr) ν (cm ⁻¹ ) 3468, 3388 (NH ₂ ), 1744 (C = 0),
The 1240 (CF) spectrum is shown in FIG. ¹ H-NMR spectrum (solvent acetone, TMS standard) δ (ppm) 8.77 (t, 1H, aromatic), 8.06
(S, 2H, aromatic), 7.04-7.00.
(M, 4H, aromatic), 6.75-6.70.
(M, 4H, aromatic), 4.73 (s, 4
H, amine) and the spectrum are shown in FIG. ¹⁹ F-NMR spectrum (solvent acetone, benzotrifluoride standard) δ (ppm) 7.25 (d, 3F, CF ₃ ), −8.15 (s, 6)
_{F, CF 3), - 9.43} (d, 6F, CF 3), - 10
4.23 (quart., 1F, CF), -106.1
6 (quart., 1F, CF) spectrum is shown in FIG. Elemental analysis table (%): as shown in Table 1.

[Table 1]

From the above, it was confirmed that the compound was the target compound. The structural formula of this compound is shown below.

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[0036]

The fluorinated aromatic diamine compound according to claim 1 is novel and is useful as a raw material for polyimide and the like, and can be produced with a high yield by the method according to claim 3.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of bis (4-benzyloxycarbonylaminophenyl ester) 5- (perfluorononenyloxy) isophthalate obtained in the example.

FIG. 2 is an IR spectrum of bis (4-aminophenyl ester) 5- (perfluorononenyloxy) isophthalate obtained in the example.

FIG. 3 is a ¹ H-NMR spectrum.

FIG. 4 is a ¹⁹ F-NMR spectrum.

Continuation of the front page (72) Inventor Yasuo Miyadera 48 Tsudai, Tsukuba, Ibaraki Prefecture Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd. (56) References JP-A-5-140338 (JP, A) JP-A-5-140450 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 219/34 C07C 213/02 C07C 269/06 C07C 271/58 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] [Chemical formula 1] [Chemical formula 1] [However, Rf in the formula, the -C _n F _2n-1 (where n 6 to 1
2), which contains one double bond, may be appropriately branched, hydrogen on the benzene ring may be appropriately substituted, and the two amino groups may be each an ester The ortho-, meta- or para-position to the bond]. 2. A compound represented by the general formula (II): [However, the general formula (II) Medium Rf, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, optionally appropriately branched The hydrogen of the benzene ring may be appropriately substituted, R ¹ is a monovalent organic group, R ² is hydrogen, and the monovalent organic group is a group for protecting an amino group; ³ OC (＝ O) -group ( where R ³ is 1
A benzyl group, a t-butyl group, a p-meth
Toxibenzyl group, p-nitrobenzyl group, p-bife
Represents a n-isopropyl group or a 9-fluorenylmethyl group.
) , An R ⁴ C (＝ O)-group (where R ⁴ represents hydrogen, an alkyl group or an aryl group), a trityl group, a p-toluenesulfonyl group, and R ¹ and R ² are 2 Value of -C
(＝ O) —C ₆ H ₄ —C (＝ O) —, wherein two nitrogen atoms are respectively bonded to the ortho, meta or para position with respect to the ester group. A fluorine-containing diamine compound in which an amino group is protected. 3. The method according to claim 1, wherein the fluorine-containing diamine compound having the amino group protected by the general formula (II) according to claim 2 is subjected to a deprotection reaction of the protecting group. A method for producing a fluorine-containing aromatic diamine compound represented by the general formula (I). [Chemical formula 3] [Chemical formula 3] [However, the general formula (III) Medium Rf, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, optionally appropriately branched And the hydrogen of the benzene ring may be appropriately substituted] with the acid chloride compound represented by the general formula (IV): [However, in the general formula (IV), R ¹ is a monovalent organic group, R ² is hydrogen, the monovalent organic group is a group for protecting an amino group, and R ³ OC (＝ O) — Group (where R ³ is a monovalent organic group
Benzyl group, t-butyl group, p-methoxyben
Jyl group, p-nitrobenzyl group, p-biphenylisop
Ropyl group, 9-fluorenylmethyl group) , R ⁴ C
(= O) - group (wherein R ⁴ represents hydrogen, an alkyl group or an aryl group), shows a trityl group, p- toluenesulfonyl group, further, R ¹ and R ^2, divalent -C (= O)-
A C ₆ H ₄ —C (＝ O) — group, wherein hydrogen on the benzene ring is
Optionally substituted, the nitrogen atom is bonded to the ortho-, meta- or para-position to the hydroxy group.) The method for producing a fluorine-containing diamine compound represented by the general formula (II), wherein the amino group is protected, according to claim 2, characterized in that: